JPH09304344A - Ionization analyzing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an analyzing device which enhances the efficiency in generating ions for use in mass spectrometry, etc. SOLUTION: A needle 22 that can move back and forth in (z)-direction is built into an ionization chamber 15, and an electrolytic solution L containing a sample is supplied into the ionization chamber 15 by a supply pipe 18. A through-hole 20 passing to the inside of the ionization chamber 15 is bored in the supply pipe 18. With a predetermined voltage applied between the supply pipe 18 and the needle 22, the end of the needle 22 is inserted into the hole 20 and contacted with the electroytic solution, to cause the ions in the electrolytic solution to cling to the end of the needle 22 through electrophoresis. After the meddle 22 has been raised, a laser beam is applied to the end of the needle 22, so that the ions clinging to the end of the needle 22 are released into the ionization chamber 15. Therefore, the ions can be enriched and converted into soft ions.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to ionization (so-called soft ionization) of biopolymers, proteins, sugar chains, DNA or drugs and other hardly volatile polymers without decomposition.
The present invention relates to an ionization analyzer for performing mass analysis of the polymer.

[0002]

2. Description of the Related Art Conventionally, in ionization analyzers for performing mass spectrometry and the like using these hardly volatile polymers as samples, techniques such as laser desorption method and electrospray method have been used to perform soft ionization of these samples. Has been.

First, a conventional ionization analyzer using the laser desorption method will be described with reference to FIG. The ion source used in the laser desorption method mixes a sample with a matrix that absorbs the irradiated laser and prevents decomposition of the sample, and coats it on the substrate 9 and dry it in the atmosphere. create. This substrate 9 is attached to an ion analyzer, and the ion analyzer is evacuated using a vacuum pump (not shown). After reaching a predetermined degree of vacuum, the laser light generated by the laser device 7 is reflected by the mirror 72 and the laser light introduction window 71.
When the ion source 8 is irradiated through the ion source 8, the ions of the matrix and the sample are evaporated. A mass spectrum is obtained by introducing these ions into the mass spectrometer 5 through the ion introducing unit 4 and detecting them by the ion detector 6. This method solves the problem that soft ionization of a sample cannot be realized because the polymer is decomposed by irradiating only the hardly volatile polymer as a sample with a laser.

Next, an ionization analyzer using the electrospray method will be described with reference to FIG. The inside diameter of the electrolyte solution L containing the sample dissociated by ions is about 10
Supply to the capillary 1 of 0 micrometer or less. The electric field generated by the high voltage applied to the capillary 1 causes the tip portion 2 of the electrolyte solution L to have a needle-like shape. Therefore, the electrolyte solution L is atomized from the tip portion 2 to have a diameter of about 1 μm. Ion droplets 3 of a certain degree are emitted to R in the atmosphere. The atmosphere R is differentially exhausted by a vacuum pump (not shown) while supplying N ₂ gas from a predetermined supply port. As shown in FIG. 30,
The ejected ion droplets 3 are fragmented or the solvent thereof is evaporated, so that the volume thereof is gradually reduced and the surface area thereof is also reduced. When the surface area of the ion droplet 3 becomes small, the ions of the sample or the ions of the solvent move to the surface of the droplet. When the volume of the droplet becomes smaller and the radius thereof reaches a predetermined critical value (about 10 nm), the Coulomb repulsive force acting between the ions in the droplet causes the ions to be ejected (so-called ion evaporation). A mass spectrum can be obtained by introducing these ions into the mass spectrometer 5 through the ion introducing unit 4 of the ionization analyzer and detecting them by the ion detector 6.

[0005]

However, in the method using the laser desorption method, the amount of the matrix becomes 10 ⁶ times as large as that of the sample, and all of this evaporates.
Efficiency ions of the sample is introduced into the mass spectrometer 10 ^-6 ~
There is a problem that it is extremely low at ^10-10 . In addition, when creating an ion source, a mixture of a matrix and a sample is applied to a substrate once to several times, dried in the atmosphere, and the substrate is attached to an ion analyzer to attach the ion analyzer. Since it was evacuated, it took a lot of time before the measurement.

In the method using the electrospray method, when the concentration of the sample with respect to the solvent is increased, the volume of the ion droplet is reduced and the radius thereof is not reduced until the critical value is reached, so that ion evaporation does not occur. There is a problem. When a non-organic solvent such as water is used,
There is a problem that the atomized ion droplet 3 is not sufficiently discharged from the tip of the capillary 1. In order to eliminate such a situation that atomization is not sufficiently performed, there is a method of increasing the electric field strength in the atmosphere and further supplying energy for atomization. However, there is a problem that discharge is likely to occur when the electric field strength is increased. Further, even by this electrospray method, not only the sample but also the solvent is entirely evaporated and the solvent is exhausted by differential evacuation, so that the efficiency of introducing the sample ions into the mass spectrometer is 10%.
There is a problem that extremely low and ^{over 6} to 10 ^{over 10.}

FD (field desorptio)
The n) method is a method in which a sample is placed on a needle and dried, the sample is inserted into a vacuum atmosphere, a voltage of several kV is applied, and ions are evaporated by an electric field generated by the application. But,
This method is not a practical method because it takes about one day to dry the sample.

Further, in order to save the complicated work of the FD method,
Eject the liquid chromatograph effluent toward the nozzle,
There is also a proposal (Japanese Patent Laid-Open No. 3-285245) to ionize the sample by applying a high voltage to the needle on which the sample is placed. However, this method also cannot be said to have high ionization efficiency of the sample, and also causes problems such as causing abnormal discharge and causing the medium itself to be ionized, which causes a background.

Therefore, an object of the present invention is that the generation of ions can be performed in a short time, the measurement time can be shortened, the ions can be measured with high sensitivity, and the ions can be introduced into a mass spectrometer. An object of the present invention is to provide an ion analyzer that can improve efficiency.

[0010]

In order to solve such an object, the present invention has the following constitution.

According to the present invention, there is provided an ionization analyzer for releasing ions of a sample contained in an electrolyte solution into the air or a vacuum in the ionization chamber, wherein a needle provided in the ionization chamber and ions in the electrolyte solution. By irradiating at least one of the adhering means for adhering the ions in the droplet or the electrolytic solution containing the droplets to the needle and the adhering droplet, the adhering ions or the needle with the laser light, It is configured to include a discharging means for discharging into the ionization chamber.

Since the needle is provided in the ionization chamber and the droplet containing the ion in the electrolyte solution or the ion in the electrolyte solution is attached to the needle, the ion can be easily taken out. Further, since at least one of the adhered droplets, adhered ions or the needle is irradiated with the laser beam, the time required for ion emission can be shortened.

Further, in the present invention, the attaching means supplies the electrolyte solution into the ion chamber and moves the needle to temporarily bring the tip into contact with the electrolyte solution, and the ionizing means in the electrolyte solution. And a means for applying a voltage of a predetermined polarity to the needle in correspondence with the charge polarity.

As described above, as the attaching means, the moving means for supplying the electrolyte solution into the ion chamber and moving the needle to temporarily bring the tip into contact with the electrolyte solution, and the charge polarity of the ions in the electrolyte solution Correspondingly, since it is configured to have a means for applying a voltage of a predetermined polarity to the needle, the tip of the needle selectively selects a droplet containing ions of a predetermined charge polarity or an ion of a predetermined charge polarity in the electrolyte solution. Since it can be attached to the substrate, highly sensitive ion analysis can be performed.

Further, in the present invention, the needle is fixed in the ionization chamber, and the adhering means moves the surface of the electrolyte solution by vibrating the supply pipe for supplying the electrolyte solution up to the vicinity of the needle. Thus, the vibrating means for adhering the electrolyte solution to the tip of the needle and the means for applying a voltage of a predetermined polarity between the supply tube and the needle corresponding to the charge polarity of the ions in the electrolyte solution may be provided.

In this way, by fixing the needle in the ionization chamber and supplying the electrolyte solution to the vicinity of the needle as an attachment means, and by vibrating the supply tube to move the surface of the electrolyte solution, the electrolyte solution is moved to the needle. It is necessary to move the needle because it has a vibrating means to be attached to the tip of the needle and a means for applying a voltage of a predetermined polarity between the supply tube and the needle corresponding to the charge polarity of the ions in the electrolyte solution. Therefore, the device can be simplified.

Further, in the present invention, the attaching means has a supply pipe for supplying the electrolytic solution to the ionization chamber, and the needle is
It may be configured to be movable forward and backward with respect to the inside of the supply pipe so that the tip portion thereof projects into the ionization chamber when moved in a predetermined direction.

Thus, the needle is provided in the ionization chamber, and the droplet containing the ion in the electrolyte solution or the ion in the electrolyte solution is attached to this needle, and the laser is attached to at least one of the attached droplet, the attached ion or the needle. Since the light is emitted, the operation is simple.

Further, in the present invention, the moving means may be constructed so that the tip of the moving means is brought into contact with the electrolyte solution temporarily by vibrating the needle.

As described above, by vibrating the needle so that its tip is temporarily brought into contact with the electrolyte solution so that droplets or ions are attached to the tip of the needle, the release of ions is repeated in a short time. You can

Further, in the present invention, the vibrating means may be an ultrasonic vibrator.

As described above, by using the ultrasonic vibrator and vibrating the ultrasonic vibrator at a predetermined frequency, the attachment of the ions to the tip of the needle is stabilized and the ions can be efficiently emitted.

Further, in the present invention, at least a part of the surface of the needle may be coated with a dielectric, an insulator, a substance that repels the electrolyte solution or a substance that adsorbs the electrolyte solution.

By coating the tip of the needle with the dielectric material as described above, ions can be efficiently attached to the tip of the needle. If it is covered with an insulator, no current will flow when attaching ions. By coating the base of the needle with a substance that repels the electrolyte, droplets can be attached only to the tip of the needle. If the tip of the needle is coated with a substance that adsorbs an electrolyte, droplets can be attached to the tip of the needle.

Further, in the present invention, the needle has a layer structure composed of an outer conductor and an inner conductor sandwiching an insulating layer at the tip of the needle, and the insulating layer at the tip of the needle is exposed. It may be configured to have.

As described above, if the needle has a layered structure composed of an outer conductor and an inner conductor sandwiching an insulating layer, and the insulating layer at the end of the needle is exposed, Since droplets and the like can be attached to the tip of, the attached droplet can be made minute.

Further, in the present invention, at least the tip portion of the needle is formed of an optical fiber, and the laser light enters from the root of the optical fiber and is guided through the inside of the needle to the needle tip portion, where the tip portion. The attached droplets or the attached ions may be irradiated.

In this way, the needle is formed of an optical fiber, laser light is made incident from the root, is guided through the inside of the needle to the tip of the needle, and the droplets or ions attached to the tip are irradiated. Therefore, it is not necessary to align the laser beam with the needle, and the laser beam can be efficiently applied to the adhered droplets or adhered ions at the tip.

In the present invention, the ionization chamber is
It may be configured as a container integrally connected to the ion analysis unit container.

In this way, the ionization chamber is formed as an airtight container integrally connected to the ion analysis unit container without differential evacuation, so that the sample ions are transferred from the ionization chamber to the mass spectrometer with high efficiency. Can be introduced at.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In the following description, an electrolyte solution refers to a so-called sample solution prepared by mixing a substance to be measured (for example, living cells and other substances) in a solvent. And In the description of the embodiment, an electrolyte solution in which the sample to be measured is dissociated into cations and anions depending on the pH concentration of the solvent is introduced, and ions of the sample to be measured are collected from this electrolyte solution to perform mass spectrometry. The ionization analysis device for discharging to the device will be described.

(First Embodiment) An embodiment in which the ionization analyzer of the present invention is applied to a TOF (time of flight) mass spectrometer will be described with reference to the drawings.

First, the schematic structure of the TOF mass spectrometer will be described with reference to FIG. A drift region 11 is provided in the ion analysis unit container 10 which is airtight and whose inside is sucked by a vacuum pump (not shown). A microchannel plate 12 having an electron multiplying function as an ion detector is disposed behind the drift region 11 so that ions incident from the front of the drift region 11 pass through the drift region 11 and the microchannel plate. It is supposed to reach twelve. Then, the detection signal S output from the anode of the microchannel plate 12 is amplified by the preamplifier 13 and then recorded by the recording unit 14 including a transient recorder capable of high-speed recording.

Next, the ionization analyzer of the present invention has a container-shaped ionization chamber 15 integrally connected to the ion analysis container 10 on the front side of the drift region 11. This ionization chamber 15 also has confidentiality. Ionization room 15
From inside the supply port 16 provided at the lower end to N ₂
Gas is supplied and exhausted from the port 17 at the upper end by a vacuum pump (not shown). A non-volatile gas may be supplied from the supply port 16 instead of the N ₂ gas. By supplying the non-volatile gas from the supply port 16, it is possible to suppress the generation of unnecessary vaporized substances and the like in the process of collecting and releasing the ions of the sample to be measured contained in the electrolyte solution. Further, the ionization chamber 15 may be in a vacuum state without supplying such a gas.

At the lower end of the ionization chamber 15, the electrolyte solution L
A supply pipe 18 for supplying the electrolyte solution L is provided, and the electrolyte solution L is supplied to the supply pipe by a syringe pump 19 or the like. A minute hole 20 communicating with the inside of the ionization chamber 15 is provided on one side of the supply pipe 18. The supply pipe may be a thin pipe.

Further, in the ionization chamber 15, a hollow cylindrical grid 21 is fixed so as to face the holes 20 with a predetermined space therebetween, and the holes 20 have a diameter of about 1 micrometer to several tens. A needle 22 that can move in the vertical direction (z direction in the drawing) within a range of about a micrometer is inserted in the hollow of the grid 21.

Since one end of the needle 22 is connected to a piezo element or an ultrasonic vibrating element built in the moving device 23, the movement of the needle 22 in the vertical direction is controlled by the operation of these elements. It A variable voltage source 24 and an ammeter 25 are connected in series between the needle 22 and the supply pipe 18. The variable voltage source 24 can control the control voltage E1 in the range of minus to plus. Therefore,
Control voltage E for increasing the potential of the supply pipe 18 relative to the needle 22
1 or supply pipe 18 to needle 22
The control voltage E1 for lowering the potential of the control voltage E1 or for controlling the needle 22 and the supply pipe 18 at the same potential.
(That is, E1 = 0 volts) can be output,
Each voltage level can also be set appropriately.

A window 81 for introducing a laser beam is provided on the side surface of the ionization chamber 15 so that the tip of the needle 22 can be irradiated with the laser beam generated by the laser device 80.

Above the grid 21, grids 27 and 28 are arranged in parallel, facing the grid 26 provided in front of the drift region 11. The grid 26 is set to the ground potential (0 volt) together with the drift region 11. Since the grids 27 and 28 are connected to the voltage source 30 controlled by the control unit 29 including a computer system, the pulse control voltages V1 and V2 (where 0 <V2 <V1) can be applied at a predetermined timing. Then, as will be described later, the ions of the sample are accumulated between the grids 27 and 28, and the predetermined pulse control voltages V1 and V2 are respectively applied to the grids 27 and 28.
Is applied to the grid 26, the cations are accelerated to the grid 26 side, are sent to the drift region 11, and are used for mass spectrometry and the like.

Further, the structure of the grids 21, 27 and 28 will be described with reference to FIG. The grid 21 is formed by forming a large number of holes by laser processing on the peripheral wall of a cylindrical tube made of an insulating material and then applying a conductive coating on the entire surface. The inner diameter of the grid 22 is
Any inner diameter can be inserted. For example, about 10 microns to about 100 microns is preferred.
Then, the upper end 21a of the grid 21 and the grid 21
A predetermined electric field gradient is generated inside the cylinder of the grid 21 by applying the voltage E2 between the lower end 21b and the lower end 21b. When treating the cations of the sample, as shown in FIG. 2, the lower end 21b is opposed to the upper end 21a.
A voltage E2 that raises the potential of is applied. When treating the anions of the sample, a voltage E2 that lowers the potential of the lower end 21b is applied with respect to the upper end 21a. The grids 27 and 28 are both formed of parallel metal nets.

FIG. 3 shows another structure of the grid 21. In FIG. 3, the grid 21 is composed of a plurality of metal rings 21c to 21e arranged in the z direction and arranged in parallel with each other at a predetermined interval. The grid 21 is configured to generate a predetermined electric field gradient in the metal rings by applying predetermined voltages E20 and E21 between the metal rings 21c to 21e. In the grid structure shown in FIG. 3, when the cations of the sample are processed, the voltage E2 is applied in order of 21c, 21d, and 21e so that the metal ring 21c has the lowest potential.
0 and E21 are applied. When treating the anions of the sample, the voltages E20, E21 are set in order of 21c, 21d, 21e so that the metal ring 21c has the highest potential.
Is applied.

The structure of the grid 21 is as shown in FIGS.
The structure is not limited to the structure shown in FIG. 2A, and any structure can be used as long as it can form an electric field gradient that draws out predetermined ions generated at the tip of the needle 22 between the grids 27 and 28. Further, the structure of the grids 27, 28 is not limited to the structure shown in FIG. 2, but any structure can be used as long as it can receive predetermined pulse control voltages V1, V2 and accelerate predetermined ions to the drift region. Good.

Next, the operation of this embodiment having such a structure will be described. Hereinafter, the case where the cations are subjected to mass spectrometry will be described as a representative. Therefore, the voltage E2 causes the lower end 21b of the grid 21 to have a high electric potential, and the upper end 21b.
A is set to a low potential.

As shown in FIG. 4, with the electrolyte solution L flowing into the supply pipe 18, the needle 22 is lowered to the hole 20 side, and the tip of the needle 22 is brought into contact with the electrolyte solution L. At this time, the polarity of the control voltage E1 is set to the supply pipe 18 with respect to the needle 22.
When the potential is set to a higher value, the cations of the sample move to the tip of the needle 22 by electrophoresis, so that the cation is concentrated and attached to the tip of the needle 22.

Next, as shown in FIG. 5, while continuing to apply E1, the needle 22 was pulled out from the hole 20 and pulled up to a predetermined height, and a high concentration of cations adhered to the tip of the needle 22. Will remain.

After that, as shown in FIG. 6A, when the tip of the needle 22 is irradiated with the laser beam generated by the laser device 80 through the window 81, the target cations are emitted together with the solvent molecules of the liquid droplets. It is preferable to irradiate the laser light in pulses. Further, the needle 22 may be pulled out from the hole 20 and pulled up to a predetermined height to irradiate the solid light after the solvent in the droplet is evaporated with the laser beam. When the needle 22 is irradiated with laser light, it may be irradiated onto a droplet or a fixed matter attached to the tip of the needle 22 as shown in FIG. 6B.
Alternatively, the needle 22 may be irradiated to the main body as shown in FIG. Further, the laser light may be applied to the needle 22 and the liquid droplet or the fixed matter, or may be irradiated to the needle 22, the liquid droplet and the fixed matter. When the body of the needle 22 is irradiated, the tip portion of the needle 22 is pulse-heated by the laser light, and the heat releases the cations in the droplet. The laser light to be applied is preferably pulsed laser light from ultraviolet rays to infrared rays, and the energy to be applied is preferably an output of several microjoules to several millijoules. When the electrolyte solution L contains a laser beam absorbing organic substance, this substance absorbs the laser beam, and thus plays a role of a buffer for preventing decomposition of the sample. Therefore, it is preferable that the electrolyte solution contains a laser beam absorbing organic substance corresponding to the laser beam to be irradiated.

The released cations move between the grids 27 and 28 due to the electric field gradient of the grid 21. After that, by applying the predetermined pulse control voltages V1 and V2 from the voltage source 30 to the grids 27 and 28, the cations existing between the grids 27 and 28 are accelerated and moved to the drift region 11. In the TOF mass spectrometer, the flight speed in the drift region 11 differs depending on the charge-to-mass ratio of the ions to be measured, so the flight time in the drift region differs. Therefore, the mass spectrum can be obtained by measuring the time of flight. That is, as a function of time from the application of the pulse control voltages V1 and V2, the cations that have reached the microchannel plate 12 are detected, and the detection signal S thereof is recorded by the recording unit 14 to obtain the mass of the sample. The spectrum is sought.

The method of attaching cations to the tip of the needle 22 is not limited to the method shown in FIGS.
For example, as shown in FIG. 7, with the electrolyte solution L flowing into the supply pipe 18, the voltage E1 is applied so that the potential of the supply pipe 18 becomes lower than the potential of the needle 22, and the needle 22
Is brought close to the liquid surface of the electrolyte solution L in the hole 20. Due to the electric field generated by the applied voltage E1, cations are attracted to the liquid surface near the needle 22 to have a high concentration. Then, the applied voltage E1 locally swells the liquid surface, and the swelling of the liquid surface (tailor cone) contacts the tip of the needle 22. In this case, the applied voltage E1 is 50V to 200V.
V is preferred. As shown in FIG. 8, the needle 22 and the supply pipe 18
When the voltage difference between them is set to zero, the liquid surface returns to the original state and high-concentration cations can be attached to the tip of the needle 22. As a method of attaching cations to the tip of the needle 22, for example, as shown in FIG. 7, a voltage E1 is applied so that the needle 22 has a low potential, and the needle 22 is moved by a moving device 23 using a piezo element. At a frequency of 10 Hz to 100 kHz, the needle 22 may be repeatedly moved in the z direction so as not to come into contact with the liquid surface. In this way, the Taylor cone develops extremely stably, and it becomes easy to attach the droplet to the tip of the needle 22. By changing this frequency, it becomes possible to control the amount of ejected ions, which was impossible in the past, and it is also possible to generate droplets of about 200 nanometers, which was impossible in the past. . Furthermore, most of the ions released in the ionization chamber can be transferred to the mass spectrometer by adjusting the vacuum exhaust amount of the ionization chamber and this frequency.

Further, as shown in FIG. 9, with the electrolyte solution L flowing into the supply pipe 18, the needle 22 is moved to the hole 20 side without applying the voltage E1 between the needle 22 and the supply pipe 18. And bring the tip of the needle 22 into contact with the electrolyte solution L,
Ions can also be attached to the tip of the needle 22 by raising the needle 22 again as shown in FIG.

As described above, in the present embodiment, in order to attach the ions to the tip of the needle 22, a predetermined voltage is applied between the needle 22 and the supply pipe 18 to attract the ions having the predetermined charge polarity. As a result, the needle 2
Can be attached to the tip of 2. Since the ions are emitted by the laser beam, it becomes possible to generate the ions in a shorter time than in the conventional case. Further, it has become possible to efficiently release ions having a predetermined charge polarity. Since the needle 22 is brought into contact with the liquid surface or the liquid surface is attracted by the voltage applied to the needle 22 to adhere the liquid droplets, the hole 20 which is the limit in the conventional electrospray method is used.
It became easy to take out the liquid droplets even when the diameter was about several micrometers.

In the description of the operation of the present embodiment, the case has been described in which the cations of the sample to be measured are sampled and released, but when measuring the anions, the control voltages E1 and E in FIG.
2 and the polarities of the pulse control voltages V1 and V2 are set opposite to the above description. That is, in the process shown in FIGS. 4 and 5, the control voltage E1 for increasing the potential of the needle 22 is applied to the supply pipe 18, and the control voltage E2 is also applied to the grid 2.
7 and 28 are applied so that the potential becomes higher than that on the supply pipe 18 side, and the pulse control voltages V1 and V2 are negative voltages (V1 <V
2 <0).

The needle 22 used in this embodiment is a metal needle having a relatively simple truncated cone-shaped tip portion as shown in FIG. 11A, but is not limited to this. Absent. For example, as shown in FIG. 11B, the tip of the needle may be covered with a dielectric film C. As shown in FIG. 11C, the entire needle may be covered with the dielectric film C. As shown in FIG. 11D, a constriction is formed between the tip and the base of the needle, and the tip of the needle is provided with a spherical portion B having a diameter slightly larger than the diameter of the constriction. Good. As a result, since the surface tension of the droplet depends on its curvature, the droplet can be attached only to the tip of the needle. As shown in FIG. 11E, the base of the needle may be coated with a hydrophobic substance such as Teflon that repels the electrolyte solution. As a result, the liquid droplets adhere only to the tip portion. Also, FIG. 11 (f)
You may use the needle which consists of a thin hollow tube as shown in FIG. As shown in FIG. 11 (g), the tip of the needle is necked, and a spherical portion B having a diameter slightly larger than the diameter of the neck is provided at the tip, and the surface of the spherical portion is a dielectric or electrolyte solution. It is also possible to coat with a film D of a hydrophilic substance that adsorbs, and the remaining portion of the tip of the needle with a film of a hydrophobic substance C that repels an electrolyte solution such as Teflon. An insulator may be used instead of the dielectric substance, or both of them may be used. As shown in FIG. 11 (h), the main body G of the needle is made of a conductor, and the tip of the needle is necked to provide a spherical portion having a diameter slightly larger than the diameter of the necked portion at the tip. The structure may be such that the surface of the needle is covered with the insulator E, and further the conductor F except the tip of the needle is covered. The needle shown in FIG. 11 (h) sets G to a low voltage with respect to F when the sample ion has a positive charge, and sets G to a high voltage with respect to F when the sample ion has a negative charge. As a result, the droplets or the ions containing the droplets are attached to the tip portion of the needle, so that the attached droplets can be made minute. Examples of substances that can be used for the needle as described above and that repel the electrolyte solution include Teflon.

As for the shape of the tip of the needle and the coating film, it is sufficient that cations or anions in the electrolyte solution L are easily attached to and released from the tip of the needle. Combinations of these modes and others The shape may be. For example, at least a part of the base surface of the needle may be coated with a substance that repels a dielectric, an insulator or an electrolyte solution, and the tip of the needle may be coated with a substance that adsorbs a dielectric, an insulator or an electrolyte solution. It may have been done. The cross-sectional shape of the needle is not limited to a circle, and may be, for example, an ellipse or a polygon such as a triangle or a quadrangle.

The diameter of the tip of the needle 22 is as shown in FIGS.
As described above, in order to keep the cations attached to the tip of the needle 22 against the mutual Coulomb force, it is desirable that the number is about 10 nanometers for about 100 cations. Generally, if the tip of the needle 22 is sharpened, the electric field is locally strengthened, and cations can be attached to the tip of the needle at a high concentration. However, the apparatus of the present embodiment is used as a general mass spectrometer. It is desirable to design the diameter of the tip of the needle 22 to be about 5 nanometers to 0.5 nanometers.

Further, in order to facilitate the attachment and release of the cations or anions in the electrolyte solution L to the tip of the needle, not only the shape of the needle is changed, but also the electrolyte solution L is changed. The structure of the supply pipe may be changed. For example, as shown in FIG. 12, the structure of the supply pipe 18 may be provided with an outlet for the electrolyte solution L in the center and an absorption port for the electrolyte solution L provided around the outlet coaxially with the outlet.

(Second Embodiment) Next, a second embodiment will be described with reference to FIG. In each component in FIG. 13, the same or corresponding portions as those in FIG. 1 are designated by the same reference numerals. Differences from the first embodiment shown in FIG. 1 will be described. At the lower end of the ionization chamber 15 of the ionization analyzer, a capillary tube 3 for introducing the electrolyte solution L into the ionization chamber is provided.
1 is provided. A thin needle 32 that can move back and forth in the z direction is inserted into the capillary tube 31. Needle 32
When the needle 32 advances to the inside of the ionization chamber 15, the tip of the needle 32 projects into the inside of the ionization chamber 15, and when the needle 32 retracts inside the capillary tube 31, the tip of the needle 32 moves to the capillary tube 31.
It is designed to be stored inside. Further, a voltage source 24 for applying a control voltage E1 having a predetermined polarity is connected between the capillary tube 31 and the needle 32.

Next, the operation of the second embodiment for analyzing cations will be described with reference to FIGS. 13 to 15 showing the cross section of the main part of the ionization analyzer. In this case, as shown in FIG. 13, the lower end of the grid 21 (needle 3
2 side) is a high potential and the upper end is a low potential E2
Is applied to provide a predetermined electric field gradient, and the voltage E3 is set so that the capillary tube 31 has a high potential with respect to the grid 21.

Next, as shown in FIG. 14, the electrolyte solution L is supplied to the capillary tube 31, and the needle 32 is moved to the inside of the ionization chamber 15. At this time, at the same time, the capillary tube 3
A control voltage E1 for applying a lower potential to the needle 32 with respect to 1 is applied. As a result, due to the electric field generated between the capillary tube 31 and the needle 32, the cations in the electrolyte solution L are electrophoresed, move to the vicinity of the tip of the needle 32, are concentrated, and are attached to the needle 32.

Next, as shown in FIG. 15, the electrolyte solution L
The tip of the needle 32 is advanced to a distance beyond the surface tension of the needle. Then, the tip end portion A of the needle 32 or the base portion B of the needle 32 is irradiated with laser light. By this laser light irradiation, the cations attached to the needle 32 are released into the ionization chamber. The positive ions move between the grids 27 and 28 due to the electric field gradient of the grid 21. After that, voltage source 3
A positive pulse control voltage V is applied to the grids 27 and 28 by 0
By applying 1 and V2, the positive ions are accelerated and flown to the drift region 11. Then, the recording unit 14 records the mass spectrum on the basis of the signal S in which the cations are detected by the microchannel plate 12.

As described above, in the second embodiment, the needle 32
Is moved into the ionization chamber 15, a predetermined control voltage E1 is applied to the needle 32 to concentrate and attach the cations of the electrolyte solution L to the tip of the needle 32, and the needle 32 is further moved to the ionization chamber 15. Since the needle 32 is irradiated with laser light to emit cations after being moved inside, the operation is extremely simple. Further, since the ions to be measured are concentrated, it is possible to solve the problem that a large amount of unnecessary electrolyte solution is ionized and the measurement is hindered as in the conventional case. further,
As shown in FIGS. 11B to 11G, the tip or the whole of the needle 32 is covered with the dielectric film 32a, and the control voltage E1 is applied to the metal portion inside the needle 32, so that the tip portion of the needle 32 is The electric field can be applied efficiently. Furthermore, if the coating film 32a is made of a material such as Teflon, the electrolyte solution attached to the tip portion of the needle 32 and the electrolyte solution L in the capillary tube 31 can be easily separated, so that ions are released. You can move quickly to the process of
The overall processing time for ion release can be reduced.

In the description of the second embodiment, the case of processing positive ions has been described, but in the case of processing negative ions, the control voltages E1 to E3 and the pulse control voltages V1 and V2 described above are used. The polarity will be set opposite to that when treating cations.

Further, as a modification of the second embodiment,
The structure of the supply pipe and the arrangement of the needles for supplying the electrolyte solution may be as shown in FIG. According to FIG. 16, a supply pipe 18 is provided instead of the capillary pipe 31 of FIG. 15, and the structure is such that an outlet for the electrolyte solution L is provided in the center of the supply pipe, and the electrolyte is provided around the outlet coaxially with the outlet. Solution L
Is provided with an absorption port. The needle 32 is arranged in the center of the outlet of the supply pipe 18 with its tip facing the direction of the ionization chamber. When the tip of the needle 32 is irradiated with laser light through the window 81 after the ions are attached to the tip of the needle 32, the ions from the tip of the needle 32 can be efficiently emitted. At this time, the atmospheric pressure at the tip of the needle may be atmospheric pressure or may be lower than atmospheric pressure. By blowing gas onto the tip of the needle, the ejected ions can be efficiently sent between the grids 27 and 28.

(Third Embodiment) Next, an embodiment of the present invention will be described with reference to FIG. In addition, in each component in FIG. 17, the same or corresponding portions as those in FIG. 1 are denoted by the same reference numerals. Differences from the embodiment shown in FIG. 1 will be described. At the lower end of the ionization chamber 15, a capillary tube 40 for introducing the electrolyte solution L is provided up to the inside thereof. Further, inside the ionization chamber 15, the tip of the capillary tube 40 that penetrates the hollow portion of the grid 21 is provided. The needle 22 is fixed so as to face the portion. The tip of the needle and the tip of the capillary tube 40 are separated by a gap of about several micrometers. Capillary tube 40
An ultrasonic transducer 41 is attached to the tip portion of the. Further, a voltage source 24 for applying a control voltage E1 having a predetermined polarity is connected between the capillary tube 40 and the needle 22.

Next, the operation of the third embodiment for analyzing cations will be described with reference to FIGS. 17 to 19 showing the cross section of the main part of the ionization analyzer. As shown in FIG. 17, a voltage E2 in which the lower end of the grid 21 (capillary tube 40 side) has a high potential and the upper end has a low potential.
Is applied to generate a predetermined electric field gradient in the grid 21.

As shown in FIG. 18, when the electrolyte solution L is supplied to the capillary tube 40 and the ultrasonic vibrator 41 is vibrated, the capillary tube 40 vibrates, so that the electrolyte solution L in the capillary tube 40 also vibrates. To do. Then, the control voltage E for setting the capillary tube 40 to a high potential and the needle 22 to a low potential
1 is applied. Due to the vibration of the ultrasonic oscillator, the liquid level of the electrolyte solution L rises to develop a Taylor cone. Then, this Taylor cone contacts the tip of the needle 22, and the cations in the electrolyte solution L are electrophoresed by the electric field by the control voltage E1 and adhere to the tip of the needle 22.
In this case, cations can be attached to the tip of the needle 22 without moving it.

As shown in FIG. 19, the vibration frequency of the ultrasonic oscillator 41 is changed so that the needle 22 is separated from the liquid surface of the electrolyte solution L. In this state, the needle 22 is irradiated with laser light to emit cations. The irradiation of the laser light may be performed on the ions attached to the tip of the needle 22, or may be performed on the base of the needle 22. The positive ions emitted by the irradiation with the laser light move between the grids 27 and 28 due to the electric field gradient of the grid 21. Positive pulse control voltages V1, V2 of the grids 27, 28 by the voltage source 30
Is applied to accelerate the positive ions to the drift region 11 and fly. The recording unit 14 records a mass spectrum based on the signal S obtained by detecting the cations by the microchannel plate 12.

As described above, in the third embodiment, the electrolytic solution L is vibrated by the ultrasonic oscillator 41 to attach cations to the tip of the needle 22, so that the needle 22 needs to be moved. Absent. Therefore, it is not necessary to adjust the position of the needle, and it is possible to simplify the device and improve the mechanical accuracy. Further, since the ions can be repeatedly attached to the tip of the needle 22 without mechanically moving the needle 22, the analysis time can be shortened. Further, when the ultrasonic oscillator is repeatedly operated, the Taylor cone is extremely stably developed on the liquid surface of the electrolyte solution L in the capillary tube 40, so that the attachment of the ions to the tip of the needle 22 is stabilized and the laser light irradiation is performed. Can efficiently release ions. Further, when the frequency of the repeated operation of laser light irradiation and the repeated frequency of the ultrasonic oscillator are made to coincide with each other and synchronized, the ions are repeatedly emitted at the frequency of the repeated operation of the ultrasonic oscillator (about 10 Hz to 10 kHz). Therefore, a large amount of ions can be generated in a short time.

In the description of the third embodiment, the case of processing positive ions has been described, but in the case of processing negative ions, the control voltages E1 and E2 and the pulse control voltages V1 and V2 described above are used. The polarity will be set opposite to that when treating cations.

As a modification of the third embodiment,
As a structure for attaching the electrolyte solution L to the needle 22,
You may make it like FIG. 20 is the same as FIG. 18 and FIG.
It is a fragmentary sectional view corresponding to. A supply pipe 18 is provided instead of the capillary pipe 40 in FIG. The supply pipe 18 is composed of two cylindrical pipes having the same central axis and different diameters, and an outlet for the electrolyte solution L is provided in the center of the end on the side of the ionization chamber 15 and an absorption port for the electrolyte solution L is provided around the outlet. Is provided. And supply pipe 1
An ultrasonic transducer 41 was fixed to the base of the blowout port of No. 8. With this ultrasonic vibrator, the end of the outlet of the supply pipe 18 can be vertically vibrated. Needle 22
The tip is fixed so as to face the outlet of the supply pipe 18. A predetermined voltage E1 is applied between the needle 22 and the supply pipe 18. Even with such a structure, the Taylor cone can be stably generated by repeatedly vibrating the ultrasonic transducer 41, and thus the ions can be attached to the needle 22. Then, the laser device 80
Ions can be emitted by irradiating the needle 22 with the laser light generated in (1) through the window 81. The ejected ions move between the grids 27 and 28 and are subjected to mass spectrometry.

(Fourth Embodiment) A fourth embodiment will be described with reference to FIG. In addition, the same or corresponding components as those of FIG. 1 of the first embodiment are denoted by the same reference numerals.
21, a capillary tube 50 for supplying N ₂ gas to the ionization chamber 15 is connected to the lower end of the ionization chamber 15, and the electrolyte solution L is supplied from a direction substantially orthogonal to the capillary tube 50. A capillary tube 51 is provided. A hole 52 having a diameter of about 1 μm to 10 μm is formed on one side of the capillary tubes 50 and 51 by laser processing or the like, so that the capillary tube 51 is ionized through the hole 52. It communicates with the inside of the chamber 15. Further, in the capillary tube 50, a hole 53 having a diameter of about 10 μm to 50 μm is formed on the side wall facing the hole 52 by laser processing or the like. The needle 22 is inserted into the hole 53, and the hole 53 and the needle 22 are sealed by the flexible sealant 54.
The gap between them is sealed. The needle 22 is a moving device 23.
It is connected to a piezoelectric element, an ultrasonic vibration element, or the like housed inside. By driving the needle 22 with these elements, the tip of the needle 22 can be inserted into or pulled out from the hole 52. Further, a voltage source 24 for applying a control voltage E1 having a predetermined polarity is connected between the needle 22 and the capillary tube 51. Further, the outer peripheral surface of the portion of the capillary tube 50 projecting into the ionization chamber 15 is covered with a coating made of a high-resistance conductive material, and the coating 55 has an upper end (on the grid 27, 28 side) and a lower end. A voltage E2 having a predetermined polarity is applied during the period. The structure of the part after the grids 27, 28 is similar to that of FIG.

The needle 22 is formed by processing the tip of an optical fiber so that a droplet of the electrolyte solution L can be attached thereto. The structure has, for example, a shape as shown in FIGS. In FIG. 22A, the core portion 56 is exposed by removing the optical fiber clad portion 57 from the tip of the needle, the tip of the needle is made spherical, and the tip portion including the tip of the needle is covered with a conductive layer 58. Is. FIG. 22 (b)
In the above, the core portion 56 is exposed by removing the optical fiber clad portion 57 from the tip of the needle, and the tip portion including the tip of the needle is further covered with the conductive layer 58. In FIG. 22C, the core portion 56 is exposed by removing the clad portion 57 of the optical fiber from the tip of the needle, and the tip of the needle is spherical. When the tip of the needle is made spherical, the surface tension of the droplet depends on the extreme rate of the droplet, and therefore the droplet adheres only to the tip of the needle. In the needles of FIGS. 22 (a) to 22 (c), when the laser light is incident from the base direction of the optical fiber toward the tip direction (arrow direction in FIG. 22), the laser light can be introduced to the tip of the needle, and the tip of the needle You can create a near field in a department.

Next, the operation of the present embodiment will be described for the case of treating cations. First, when the electrolyte solution L is supplied by the capillary tube 51 and the tip of the needle 22 is inserted into the hole 52, the tip of the needle 22 comes into contact with the charge solution L. At this time, the capillary tube 51 is attached to the needle 22.
When the polarity of the control voltage E1 is set so as to increase the potential of the positive electrode, the cations are concentrated and attached to the tip of the needle 22.

Next, the needle 22 is retracted from the hole 52, and the tip of the needle 22 is separated from the liquid surface of the electrolyte solution L. Laser light generated by the laser device 80 is guided to the base of the needle 22 by an optical fiber or the like, and the laser light is incident on the needle 22. The cations adhering to the tip of the needle 22 are converted into the capillary tube 5 by the evanescent light or the direct light by the incident laser light.
It is released within 0. The ejected ions are moved between the grids 27, 28 by the electric field gradient generated by the voltage E2 and the conductive coating 55. Grid 27, 28
When the pulse control voltages V1 and V2 are applied to, these ions are introduced into the drift region 11.

When the cations attached to the tip of the needle 22 are released, in order to prevent evaporation of the electrolyte solution attached to the tip, the gas supplied from the capillary tube 50 has the same quality as the solvent. It is desirable to include water vapor or the like. Further, the degree of vacuum of the ionization chamber in this embodiment is estimated as follows. For example, a capillary tube 50 having an inner diameter of 30 μm and a length of 1 cm
Is applied, the gas leak amount Q is 4 × 10
^-3 (Torr.l / sec), and ionization chamber 1
When pumping speed V of the vacuum pump for exhaust connected to the 5 and 100 (l / sec) ~1000 ( l / sec), the internal pressure of the ionization chamber, Q / V = 4 × 10 ^over 6-4
Since it becomes × 10 ⁻⁵ (Torr), the ionization chamber 15 can be sufficiently vacuumed.

Further, the distance from the gas introduction end of the capillary tube 50 to the hole 52 is shortened so that the pressure at the position of the hole 52 is brought close to the pressure (1 atm) at this gas introduction end. It is desirable to suppress the evaporation of L.

(Fifth Embodiment) A fifth embodiment will be described with reference to FIG. The same or corresponding components as those of the first embodiment are designated by the same reference numerals. FIG.
3, the difference from the first embodiment will be described. The capillary tube 60 for accommodating the needle 22 is the ionization chamber 1
5, the lower end of the capillary tube 60 is connected to the hole 20 formed in the supply pipe 18, the other end communicates with the supply port 16, and the upper end is opened facing the grids 27, 28. There is. A laser beam introduction window 82 is provided on the side surface of the capillary tube 60. Further, the outer surface of the capillary tube 60 is coated with a high-resistance conductive film 61, and by applying a voltage E2 of a predetermined polarity to the upper and lower ends of the conductive film 61, the capillary tube 60 is made hollow inside. An electric field gradient is generated.

In the present embodiment having such a configuration, as in the first embodiment, the voltage E1 and the voltage E2 are set to predetermined polarities so that the ions of the electrolyte solution L are attached to the needles 22 and the laser light is irradiated. By doing so, the ions can be released and subjected to mass spectrometry.

(Sixth Embodiment) A sixth embodiment will be described with reference to FIG. It should be noted that the same or corresponding components in FIG. 17 of the third embodiment and FIG. 23 of the fifth embodiment are denoted by the same reference numerals. In FIG. 24, the third,
Differences from the fifth embodiment will be described. Ionization room 15
A capillary tube 40 for supplying the electrolyte solution L is connected to the lower end of the, and an ultrasonic transducer 41 is fixed to the tip portion of the capillary tube 40. In addition, the needle 22
Is provided in the ionization chamber 15, the lower end of the capillary tube 60 faces the upper end of the capillary tube 40, the other end of the capillary tube 60 communicates with the supply port 16, and the capillary tube 60 The upper end of 60 is open facing the grids 27, 28. A laser beam introduction window 82 is provided on the side surface of the capillary tube 60. Further, the outer surface of the capillary tube 60 is covered with a high resistance conductive film 61. Then, a predetermined electric field gradient is generated inside the hollow of the capillary tube 60 by applying a voltage E2 having a predetermined polarity to the upper and lower ends of the conductive film 61.

Also in the present embodiment having such a configuration, similarly to the third embodiment or the fifth embodiment, the voltage E1 and the voltage E2 are set to a predetermined polarity to vibrate the ultrasonic transducer 41. As a result, the ions of the electrolyte solution L can be attached to the tip of the needle 22 with the needle 22 fixed. Then, by irradiating with laser light, attached ions can be released to the tip of the needle and can be used for mass spectrometry.

(Seventh Embodiment) A seventh embodiment will be described with reference to FIG. Note that constituent elements that are the same as or correspond to those in FIG. 13 of the second embodiment and FIG. 23 of the fifth embodiment are denoted by the same reference numerals. In FIG. 25, the second,
Differences from the fifth embodiment will be described. Ionization room 15
A capillary tube 31 for supplying the electrolyte solution L is connected to the lower end of the. A needle 32 that can move back and forth is inserted into the capillary tube 31. Further, a capillary tube 60 extending from the lower end to the grids 27, 28 side is provided in the ionization chamber 15, and one end of the capillary tube 60 communicates with the supply port 16. The outer surface of the capillary tube 60 is covered with a high resistance conductive film 61. Then, a voltage E2 of a predetermined polarity is applied to the upper and lower ends of the conductive film 61 to generate an electric field gradient inside the hollow inside of the capillary tube 60.

In this embodiment having such a configuration, as in the second and fifth embodiments, when the voltage E1 and the voltage E2 are set to a predetermined polarity, the needle 32 is moved to move the ions of the electrolyte solution L. It can be attached to the tip of the needle 32. Then, by irradiating with laser light, the attached ions can be released and used for mass spectrometry.

As described above in the first to seventh embodiments, the ionization analyzer of the present invention can be integrated with a mass spectrometer or the like, so that the released ions can be directly analyzed by the mass spectrometer. Therefore, extremely high transfer efficiency can be obtained.

In the above description of the embodiments, the case where the present invention is applied to the TOF mass spectrometer has been described, but the application of the present invention is not limited to the TOF mass spectrometer, and for example, 4 It can also be applied to a deuterium mass spectrometer and the like.

(Eighth Embodiment) An eighth embodiment will be described with reference to FIG. In addition, the same or corresponding components as those of FIG. 1 of the first embodiment are denoted by the same reference numerals.
In FIG. 26, differences from the first embodiment will be described. A capillary tube 40 for supplying an electrolyte solution is provided on the lower side surface of the ionization chamber 15. A hole 43 is formed at a position facing the capillary tube 40 on the inner surface of the ionization chamber 15. The needle 22 is inserted into the hole 43 with its tip facing the capillary tube 40, and the gap between the hole 43 and the needle 22 is sealed by the flexible sealing material 44. The needle 22 is connected to a piezo element housed in a moving device 23. A supply pipe 16 for supplying N ₂ gas is provided on the bottom surface of the ionization chamber 15. A window 81 for introducing laser light is provided on the side surface of the ionization chamber 15 in order to irradiate the tip of the needle 22 with laser light. Further, in the ionization chamber 15, a skimmer 90 is provided below the grids 27 and 28 and above the needle 22, and separates the ionization chamber 15 into an ion emission chamber 91 and an ion accumulation chamber 92.

Next, the operation of this embodiment will be described. The electrolyte solution L is supplied to the capillary tube 40, and the needle 22
The control voltage E1 is applied to. Further, when an oscillating voltage is applied to the piezoelectric element housed in the moving device 23, the needle 2
2 vibrates and the distance from the liquid surface of the electrolyte solution changes, so that Taylor cones are periodically generated on the liquid surface,
Sample ions or droplets containing sample ions adhere to the tip of the needle 22. In this state, when laser light is applied to the adhered droplets at the tip of the needle 22 or the adhered ions or the solid matter after adsorbing the droplets, the ions are emitted. It is preferable to irradiate this laser light in pulses. Further, in order to favorably perform soft ionization of the sample, the electrolyte solution L
For this purpose, it is desirable to mix a solvent that absorbs laser light and prevents decomposition of the sample. The ions thus generated pass through the skimmer 90 and are introduced into the TOF mass spectrometer. As an introduction method, N ₂ gas may be blown off from the supply pipe 16 or may be introduced without blowing N ₂ gas. Here, the ion emitting unit 91 is preferably at atmospheric pressure.

As a modification of the eighth embodiment,
You may make it like FIG. In FIG. 27, a skimmer 93 is provided in the ionization chamber 15 of FIG.
It is separated into. The differential exhaust chamber 94 has a port 95.
Is evacuated by a low vacuum pump (not shown).

Here, in the embodiment of FIGS. 1 to 25, the skimmer 9 as shown in FIGS. 26 and 27 is used.
Although 0 and 93 are not provided, a skimmer or a thin tube may be introduced as in the conventional case. further,
Differential exhaust may be performed. In this case, the amount of ionized sample ions can be controlled by the frequency of vibration of the needle 22. For example, when it is desired to introduce all the ions to be ionized into the TOF mass spectrometer, the frequency of the needle 22 may be lowered.

[0088]

According to the present invention as described above,
A needle is provided in the ionization chamber, and the sample ion of the electrolyte solution L, the droplet containing the sample ion, or the solid matter of the droplet containing the sample ion is attached to the tip of the needle, and the solid substance of the droplet is irradiated with laser light to emit the ion. Since the ions are emitted, the ions of the sample to be measured can be easily obtained in a short time, and the ion analyzer capable of shortening the time of ion analysis can be provided.

Further, a needle is provided in the ionization chamber, and the sample ion of the electrolyte solution L, the droplet containing the sample ion, or the solid substance of the droplet containing the sample ion is attached to the tip of the needle.
Since this is irradiated with laser light to emit ions, it is possible to easily and repeatedly obtain the ions of the sample to be measured, and it is possible to provide an ion analyzer capable of continuous operation. Became.

Further, a needle is provided in the ionization chamber, and the sample ion of the electrolyte solution L, the droplet containing the sample ion, or the solid substance of the droplet containing the sample ion is attached to the tip of the needle.
Since this is irradiated with laser light to emit ions, a small amount of ions can be emitted, and higher ion transfer efficiency can be achieved as compared with the conventional case. As a result, the efficiency of introduction into the mass spectrometer is increased, and a highly sensitive ion analyzer can be provided.

Furthermore, a needle is provided in the ionization chamber, and a predetermined voltage is applied to the tip of the needle to apply a predetermined charge polarity ion in the electrolyte solution L to the tip of the needle, or a droplet containing a sample ion, or Depositing a solid of droplets containing sample ions,
It was designed to emit ions by irradiating it with laser light, so the ions that were concentrated and attached to the tip of the needle were released,
Higher precision ion analysis than before has become possible.

Further, since the ionization chamber and the ion analysis container including the mass spectrometer are integrated and the differential pumping system is eliminated to control the amount of the solution to be ionized, all the sample ions and The solvent vapor and the incident N ₂ gas can be introduced into the TOF mass spectrometer, and the sample ions can be introduced from the ionization chamber to the mass spectrometer with high transfer efficiency.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing a configuration of a first embodiment of an ion analyzer of the present invention.

FIG. 2 is a perspective view showing a configuration of a grid in FIG.

FIG. 3 is a perspective view showing another configuration of the grid in FIG.

FIG. 4 is a partial cross-sectional view illustrating the operation of the first embodiment.

FIG. 5 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 6A is a partial cross-sectional view further illustrating the operation of the first embodiment. FIG. 6B is an enlarged perspective view for explaining irradiation of laser light on the needle. FIG. 6C shows
It is an expansion perspective view for demonstrating irradiation of a laser beam to a needle.

FIG. 7 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 8 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 9 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 10 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 11 is a partial cross-sectional view showing the shape of the needle provided in the embodiment.

FIG. 12 is a partial cross-sectional view further explaining the operation of the first embodiment.

FIG. 13 is a vertical cross-sectional view showing the configuration of the second embodiment of the ion analyzer of the present invention.

FIG. 14 is a partial cross-sectional view illustrating the operation of the second embodiment.

FIG. 15 is a partial cross-sectional view further explaining the operation of the second embodiment.

FIG. 16 is a partial cross-sectional view further explaining the operation of the second embodiment.

FIG. 17 is a vertical cross-sectional view showing the configuration of the third embodiment of the ion analyzer of the present invention.

FIG. 18 is a partial cross-sectional view illustrating the operation of the third embodiment.

FIG. 19 is a partial cross-sectional view further explaining the operation of the third embodiment.

FIG. 20 is a partial cross-sectional view further explaining the operation of the third embodiment.

FIG. 21 is a vertical cross-sectional view showing the configuration of the fourth embodiment of the ion analyzer of the present invention.

FIG. 22 is a partial cross-sectional view showing the shape of the needle provided in the embodiment.

FIG. 23 is a vertical cross-sectional view showing the configuration of the fifth embodiment of the ion analyzer of the present invention.

FIG. 24 is a vertical cross-sectional view showing the configuration of the sixth embodiment of the ion analyzer of the present invention.

FIG. 25 is a vertical cross-sectional view showing the configuration of the seventh embodiment of the ion analyzer of the present invention.

FIG. 26 is a vertical cross-sectional view showing the configuration of the eighth embodiment of the ion analyzer of the present invention.

FIG. 27 is a vertical sectional view for explaining the operation of the eighth embodiment.

FIG. 28 is a cross-sectional view showing the configuration of a conventional ion analysis apparatus by the laser desorption method.

FIG. 29 is a cross-sectional view showing the configuration of a conventional ion analysis apparatus by the electrospray method.

FIG. 30 is an explanatory diagram for explaining a problem of the conventional ionization analyzer.

[Explanation of symbols]

15 ... Ionization chamber, 18 ... Supply pipe, 20, 33 ... Hole, 2
1, 27, 28 ... Grid, 22, 32 ... Needle, 23 ... Moving device, 24 ... Voltage source, 31, 40, 50, 60 ... Capillary tube, 41 ... Ultrasonic transducer, 80 ... Laser device

Claims (10)

[Claims] 1. An ionization analyzer for releasing ions of a sample contained in an electrolyte solution into air or a vacuum in an ionization chamber, wherein a needle provided in the ionization chamber and ions in the electrolyte solution are provided. A droplet containing or an attachment means for attaching ions in the electrolyte solution to the needle, and by irradiating at least one of the attached droplet, the attached ion or the needle with a laser beam, An ionization analysis device, comprising: a release unit configured to release the ions or the attached ions into the ionization chamber. 2. The adhering means supplies the electrolyte solution into the ion chamber and moves the needle to temporarily bring the tip thereof into contact with the electrolyte solution, and a moving means in the electrolyte solution. The ionization analyzer according to claim 1, further comprising: a unit that applies a voltage having a predetermined polarity to the needle corresponding to a charge polarity of the ions. 3. The needle is fixed in the ionization chamber, and the adhering means moves the surface of the electrolyte solution by vibrating the supply pipe for supplying the electrolyte solution to the vicinity of the needle. By doing so, a vibrating means for attaching the electrolyte solution to the tip of the needle, and means for applying a voltage of a predetermined polarity between the supply pipe and the needle corresponding to the charge polarity of the ions in the electrolyte solution. The ionization analyzer according to claim 1, further comprising: 4. The supply means has a supply pipe for supplying the electrolyte solution to the ionization chamber, and the needle is provided in the supply pipe so that a tip of the needle projects into the ionization chamber when the needle moves in a predetermined direction. The ionization analyzer according to claim 1, wherein the ionization analyzer is provided so as to be movable back and forth. 5. The ionization analyzer according to claim 2, wherein the moving means vibrates the needle to temporarily bring its tip into contact with the electrolyte solution. 6. The ionization analyzer according to claim 3, wherein the vibrating means is an ultrasonic oscillator. 7. The needle according to claim 1, wherein at least a part of the surface of the needle is coated with a dielectric, an insulator, a substance that repels an electrolyte solution or a substance that adsorbs the electrolyte solution. Ionization analysis measures. 8. The needle has a layered structure consisting of an outer conductor and an inner conductor sandwiching an insulating layer at the tip of the needle, and the insulating layer at the tip of the needle is exposed. The ionization analysis device according to claim 1, wherein 9. The needle has at least a tip portion formed of an optical fiber, and the laser light is incident from a root of the optical fiber,
The ionization analyzer according to claim 1, wherein the ionization analyzer is guided through the inside of the needle to the tip of the needle, and the attached droplet or the attached ion at the tip is irradiated. 10. The ionization analyzer according to claim 1, wherein the ionization chamber is formed as a container integrally connected to an ion analysis unit container.